Anthraquinone derivatinves and process of preparing the same



Patented May 26, 1936 ANTHRAQUINONE DERIVATIVES AND PROC- ESS OF PREPARING THE SAME Alexander J. Wuertz, Carrollville, Wis, assignor to E. I. du Pont de Nemours & Company, wihmngton, Del., a corporation of Delaware No Drawing. Original application May 21, 1929,

Serial No. 364,943. Divided and this application September 14, 1932, Serial No. 633,082

10 Claims.

This application is a division of my 'copending application, Ser. No. 364,943, filed May 21, 1929.

The invention herein set forth relates to new .anthraquinone derivatives which are useful as intermediates for vat dyestufis. More particularly, it relates to carbonyl chlorides of the anthraquinone-acridones derived from the dicarboxylic acid derivatives of anthraquinone described in said parent application, Ser. No. 364,943, upon treating with a condensing agent, as thionyl chloride or phosphorous pentachloride and heating, and which are typified by the formula:

wherein one of the substituents X, Y and Z represents the group The prior art patents German #237,236; British #894 of 1911; French #425,859 and United States #1,0l1,068 deal with the condensation products of halogen-anthraquinone derivatives with primary amino derivatives where one but not both derivatives contains a carboxylic acid group. The resultant products thus obtained have the following general structures:

where the carboxylic acid groups are in the orthoposition to the (-NH) radical regardless of whether the groups are in the anthraquinone nucleus or in the substituent radical (R).

Furthermore, it is of general knowledge in the field of anthraquinone chemistry that, when there following example:

Other examples could be given. However, these will suffice for illustrating the fundamental principles under consideration.

The acridone dyes prepared from such intermediates, however, with the possible exception of two or three, have poor covering power on the fiber and furthermore they have a tendency to bleed, which, obviously, is a disadvantage.

This being the present state of the art, the primary object of the present invention is therefore the preparation of vat dyes of the anthraquinone-acridone type which are free from the objections common to the dyes of this type heretofore known. Another object is the preparation of intermediates from which the new dyes may be prepared.

With these objects in View I conceived the idea that if a new anthraquinone derivative could be prepared which had a carbonyl chloride grouping, it would be possible to prepare a new line of valuable 'colors which would have the advantages of both an acridone as well as a carbonyl-imid structure. The anthraquinone-acridone molecule was deemed suitable for this purpose.

These objects are accomplished by the following discoveries:

When l-halogen-anthraquinone-2carboxy1ic acid is condensed With such aromatic primary amino-carboxylic acids as anthranilic, metaand para-amino-benzoic acids or naphthyl-aminocarboxylic acids in a medium of an alkaline solutive aromatic amino-carboxylic acid from which they may be derived:

il (1) O i l 0A Metaderivative.

V O OK 0 OH II 011 M O a w Para-derivative.

As already noted, the foregoing compounds by virtue of having one carboxylic acid group in the ortho position to the (-NH) linkagearecapable of forming anthraquinone acridones when treated with such condensing agents as an excess of thionyl chloride or a slight excess of phosphorous pentachloride, or other suitable condensing agents, in a medium of an inert solvent such as ni'trobenzene, solvent naphtha, dichlorobenzene or toluene.

When a suitable chloride is employed as the condensing agent before the ring closure takes place the dicarbonyl-chloride is formed which, when heated, passes 'over to the acridone structure, the reaction being accompanied by an elimination of hydrogen chloride. 1 Under these conditions the carbonyl chloride group in the substituent nucleus remains intact in a stable condition. The resultant compound'from such a chemical reaction, when the condensation productt from 1-chloro-anthraquinone-2-carboxylic acid and para-amino-benzoic acid is used, would be the carbonyl-chloride of 2,1-anthraquinonyl-- ene-phenyl-acridone which has the following configuration:

Ortho-derivative.

The latter structural formula indicates that I have a simple anthraquinonylene-acridone, wellknown in the field of anthraquinone chemistry, plus a carbonyl-chloride radical which constitutes a new and novel substituent. It is this group or radical which confers entirely new physical and chemical properties upon the molecule. This acid-chloride gr p is capable of reacting with strong and weak bases and salts such as the primary amine derivatives of both the aliphatic and aromatic series, including the amines of the anthraquinone type and many others.

The chemical behavior of these anthraquinonephenyl-acridone-carbonyl chlorides is of unusual importance to the synthesis of new vat dyes. They will readily condense with aliphatic and aromatic primary amines to form pink and violet colors. Furthermore, they lend themselves quite readily to simple condensations with all the amino derivatives of anthraquinone, producing colors which fall into the fast orange shades.

The invention will now be described more pa ticularly as to its various phases.

Di-carbomylic acid derivatives of anthraquinone As already indicated the first s'tep in the p'repa ration of thenew dyes involves the preparation: of the di-carboxylic acid derivatives of anthrai quinone. The following examples will illustrate the general procedure for the derivation of the aforesaid compounds.

Example 1.200 parts of l-chloro-anthraquinone-2-carboxylic acid and -110 parts of para-' amino-benzoic acid are suspended in 2000-2500 parts of water. This suspension is then made alkaline with a sufficient quantity of caustic soda (solid or solution) to just turn the solution to the alkaline side. Both of the carboxylic acids will go into solution under these conditions. To this solution are then added 600-800 parts of sodium or potassium carbonate and 25-50 parts of cupric chloride and the whole is heated to the boiling point (IOU-104 C.) and maintained at this point for a period of six to eight hours, or until no further deepening of the color takes place. The solution is then diluted with twice its original volume of hot water andfiltered directly. The filtrate will contain the dicarboxylic acid sought and the residue will consist of copper salts and small amounts of by-products of an indefinite constitution. In order to isolate the free acid it is only necessary to acidify the filtrate with a mineral acid such as dilute hydrochloric or dilute sulphuric acid and by filtering off the precipitate a pure product is obtained which, after drying, is an orange-red powder, soluble in alkaline solution and insoluble in dilute acids, but soluble in strong sulphuric acid (colorless or slightly yellow solution).

Instead of using para-amino-benzoic acid, meta-amino-benzoic acid and ortho-aminobenzoic acid as well as the amino naphthoic acids may be used under the conditions similar to those described above, whereupon the corresponding dicarboxylic acids are obtained.

Example -2.200 parts of l-chlor-anthraquinone-Z-carboxylic acid and -420 parts of para-amino-salicylic acid are suspended in 2000- 2500 parts of water and made alkaline as indicated in Example 1. 600-800 parts of sodium carbonate are then added, followed by 25-50 parts of cupric chloride and the charge is heated,

in the same manner as in the previous example. Under these conditions there is obtained a dicarboxylic acid which contains a hydroxyl group in the phenyl-amine nucleus. This product has the following configuration:

and consists of a violet powder, extremely soluble in an alkaline solution and in general has similar properties to the products described in Example 1. Instead of using para-amino-salicylic acid the isomeric metaand ortho-derivatives may be used, thus arriving at the respective isomeric hydroxy-dicarboxylic acids.

In the above examples the cupric chloride is employed as a catalyst for the reaction.

Anthmquz'none carbonyl chlorides In order to obtain the anthraquinone carbonyl chlorides, it is only necessary to subject the dicarboxylic acid derivatives of anthraquinone obtained as just described to the action of a condensing agent of the type of thionyl chloride or phosphorous pentachloride in an inert solvent. The complex reactions involved may be expressed in the following manner in the case where 2-carboxy-l-anthraquinonyl amino-para-phenyl-carboxylic acid is employed as the intermediate:

0 l H 4 OH \Q-i- 2PC15 The resultant new compound is 2,1-anthraquinone-phenyl-acridone-paracarbonyl chloride. If the corresponding orthoor the meta-carbonylchlorides are desired it is only necessary to take the respective isomeric carboxylic acid derivatives and subject them to a similar treatment. The most valuable product, however, is the compound in which the residual carbonyl chloride group is in the para-position.

The following examples are furnished for the purpose of illustrating this type of compound.

Example 3.-200 parts of l- (4'-carboxyanilino) Z-carboxyanthraquinone as obtained in Example 1, are suspended in 800 to 1000 parts of nitrobenzene under good agitation. To this suspension are added, in a period of one-half to one hour, 250 parts of anhydrous phosphorous pentachloride. The reaction takes place without any external heating and the dicarboxylic acid is converted to the dicarbonyl chloride. (This product may be isolated if desired). After one to two hours of vigorous agitation the reaction mass is slowly heated to 90-100 C. and maintained at this point for a period of two hours or until no further reaction takes place.

During the course of the heating at 90-l00 C. the carbonyl chloride group in the anthraquinone ring enters into a reaction with the phenyl-nucleus to form the acridone configuration. This is accompanied by a loss of hydrogen chloride. The carbonyl chloride in the para-position in the phenyl-group remains intact.

If the corresponding orthoand meta-carboxylic acids are used under identical conditions the respective acridone-carbonyl chlorides are formed. These have analogous structures, being isomeric with the former product:

C on t FQ Y O Ortho-derivative 0 0 EN 0\ o1 Meta-derivative Example 4.200 parts of 1-(4-carboxyanilino) Z-carboxyanthraquinone as obtained in Example l, are suspended in 1000 parts of solvent naphtha under good agitation. To this suspension are added 250 parts of anhydrous phosphorous pentachlori-de. From this point the procedure is as indicated in Example 3. The final product is identical with the product obtained in the previous example.

Example 5.200 parts of l-(4'-carboxyanilino) -2-carboxyanthraquinone are suspended in 1000 parts ofsolv-ent naphtha. To this suspension are added 400 parts of thionyl chloride and the suspension, under good agitation, is heated under a reflux at to C. for eight hours. Then, under distillation of the excess of thionyl chloride, the temperature is raised to -120 C. for a period of two to three hours. The reaction mass is allowed -0001 to 20-30 C. and isolated in the same manner as indicated in Example 3. The final product is identical with the product obtained in the previous examples.

The compounds so obtained are new intermediates of particular value in the preparation of the group of new dyes disclosed in parent application, Ser. No. 364,943.

It is to be understood that the above examples are presented for purposes of illustration only and that applicant does not intend to be limited to the particular reagents and conditions therein specified.

Thus, instead of carrying out the preparation of the anthraquinone-carbonyl-chlorides in a single step as described in Examples 3, 4 and 5, the dicarbonyl chloride, Which is formed at room temperature, may be isolated by filtration and then, by further suspending this product in half the amount of solvent used originally and subsequent heating to 90.-100 C., it is converted to the pure carbonyl chloride. Solvent naphtha, dichlorobenzene, toluene and xylene may be substituted for nitrobenzene in the first example. The best results, however, are obtained with the use of either nitrobenzene or solvent naphtha.

Also instead of the phosphorous pentachloride and thionyl chloride employed as the condensing agent in Examples 3, 4 and 5, other suitable chlorides may be employed as, for example, benzotrichloride.

Furthermore, it will be understood that the compounds employed in the preparation of the dicarboxylic acid derivatives of anthraquinone may'contain substituent groups in the aryl nuclei, such, for example, as halogen. It, of course, follows that the anthraquinone carbonyl chlorides may contain corresponding substituents.

As many apparently widely different embodiments of this invention may be made without departing from the spirit thereof, it is to be understood that I do not limit myself to the foregoing examples or description except as indicated in the following claims.

I claim:

1. A compound represented by the formula:

wherein R represents an aryl radical of the benzene or naphthalene series to which the NH and CO groups are connected in ortho position.

2. A compound of the type set forth in claim 1, wherein R represents a benzene nucleus.

3. A compound of the type set forth in claim 1, wherein R represents a benzene nucleus and the group is in the para position to the amino group.

4. The process of preparing a dyestuff intermediate which comprises heating in an inert organic solvent a compound represented by the formula:

wherein R represents an aryl radical of the benzene or naphthalene series, and a chlorinating agent of the type which is adapted to convert a carboxylic acid into a carbonyl chloride.

5. A compound of the type set forth in claim 1 wherein R represents a naphthalene nucleus.

6. The process of preparing an intermediate for dyestuffs which comprises heating in an inert organic solvent a compound of the type )k COOH COOH and a chlorinating agent of the type which is adapted to convert a carboxylic acid into a carbonyl chloride.

7. The process of preparing a compound of the anthraquinone-acridone series which comprises reacting upon a compound of the general formula:

COOH

wherein R is an aryl radical of the benzene or naphthalene series, in an inert organic solvent, with a chlorinating agent of the type which is adapted to convert a carboxylic acid into a carbonyl chloride, to produce a compound of the general formula OOC1 COOH

wherein R is an aryl radical of the benzene or naphthalene series, in an inert organic solvent, with a chlorinating agent of the type which is adapted to convert a carboxylic acid into a carbonyl chloride, to produce a compound of the general formula n I [D m1 wherein R has the same significance as above, and heating the latter compound in an inert organic solvent at a temperature of about 90 to 100 C. to form the acridone ring.

9. An anthraquinone-arylene-acridone of the 70 class consisting of anthraquinone-Z,l-benzacridones and .anthraquinone-Z,l-naphthacridones which contain a carbonyl chloride group in the arylene radical.

10. In the process for preparing dyestuff intermediates, the step which comprises reacting a wherein R represents an aryl radical of the hencompound having the general formula zene or naphthalene series, in an inert organic O HN R COOH solvent with a chlorinating agent of the type [1 which is adapted to convert a carboxylic acid into a carbonyl chloride.

\% ALEXANDER. J. WUERTZ. 

